Process and accompanying catalysts for the hydroformylation of formaldehyde to glycol-aldehyde

ABSTRACT

A process and accompanying catalyst for the hydroformylation of formaldehyde to glycol aldehyde is disclosed. The process features the utilization of (1) a class of transition metal phosphine-amide complexes, (2) a class of transition metal phosphine-amine complexes, and (3) mixtures of 1 and 2 as particularly suitable for use.

This application is a continuation-in-part of Ser. No. 596,994, filedApr. 5, 1984, now U.S. Pat. No. 4,560,806 which is acontinuation-in-part of Ser. No. 508,704, filed June 28, 1983 nowabandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is related to a process and accompanying catalyst for thepreparation of glycol aldehyde, and more particularly is related to thepreparation of glycol aldehyde from the reaction of formaldehyde, carbonmonoxide and hydrogen in the presence of (1) at least one member of aclass of rhodium phosphine-amide catalysts in the presence of a widevariety of organic solvents, or (2) at least one member of a class ofrhodium phosphine-amine catalysts, either with or without an excess of atriarylphosphine, and also in the presence of a wide variety ofsolvents, or (3) a wide variety of mixtures of members of classes (1)and (2). The glycol aldehyde product is later hydrogenated to ethyleneglycol.

2. Description of the Prior Art

Glycol aldehyde is a valuable intermediate in many organic reactions,and is particularly useful as an intermediate in the production ofethylene glycol through a catalytic hydrogenation process.

Ethylene glycol is a valuable commercial chemical with a wide variety ofuses, e.g., as a coolant and antifreeze, monomer for polyesterproduction, solvent, and an intermediate for production of commercialchemicals.

The reaction of formaldehyde with carbon monoxide and hydrogen in thepresence of a variety of catalysts at elevated temperatures andsuperatmospheric pressures is a well known reaction and yields glycolaldehyde, together with methanol, as well as lesser amounts ofpolyhydroxy compounds which can be subsequently separated by properseparation procedures. For example, U.S. Pat. No. 2,451,333 describesthe reaction of formaldehyde, carbon monoxide and hydrogen over a cobaltcatalyst to produce ethylene glycol. U.S. Pat. No. 3,920,753 disclosesthe production of glycol aldehyde by the reaction of formaldehyde,carbon monoxide and hydrogen in the presence of a cobalt catalyst undercontrolled reaction conditions; however, the process produces relativelylow yields of product. Japanese Pat. No. J57-118,527 describes theproduction of glycol aldehyde using a ruthenium catalyst system.European Pat. No. 002,908 describes a process for the production ofglycol aldehyde from the reaction of formaldehyde, in the presence of arhodium-triphenyl phosphine ligand catalyst, with carbon monoxide andhydrogen, in a tertiary amide solvent. This reference further suggeststhat glycol aldehyde is preferably extracted from a water immisciblehydroformylation solvent. However, the proposed method suffers from thedrawback of limiting the choice of hydroformylation solvent to the classof water immiscible solvents, whereas the most effectivehydroformylation solvents, such as acetonitrile, are very water soluble.Furthermore when extracting glycol aldehyde with an aqueous extractant,even when using a water immiscible solvent, a substantial amount of theexpensive rhodium catalyst migrates into the water phase and is lost,thereby decreasing the amount and the resultant activity of theremaining catalyst.

U.S. Pat. No. 4,291,179 describes a similar reaction for the productionof acetaldehyde in which trifluoroacetic acid is added to produce glycolaldehyde. U.S. Pat. No. 4,356,332 describes the preparation of ethyleneglycol from the reaction of synthesis gas and formaldehyde, using arhodium or cobalt catalyst in the presence of a substantially inert,oxygenated hydrocarbon solvent. European Patent Application 82/200,272.1describes a process for the preparation of glycol aldehyde whichcomprises reacting formaldehyde, hydrogen and carbon monoxide in thepresence of either a rhodium or cobalt containing catalyst precursor,together with a strong protonic acid, a tertiary amide solvent and atriaryl phosphine, U.S. Pat. No. 4,200,765 describes a process ofpreparing glycol aldehyde involving reacting formaldehyde, carbonmonoxide, and hydrogen in a tertiary amide solvent in the presence of acatalytic amount of rhodium in complex combination with carbon monoxide,using triphenyl phosphine as the preferred catalyst promoter. U.S. Pat.No. 4,405,814 discloses a related process for the production of glycolaldehyde, such process appearing to be as close to applicant'sphosphine-amine system as anything currently known, which incorporates atertiary organophosphorous or arsenic moiety into the rhodium catalystcomplex, together with a basic organo amine having a pKa of at least1.0. The process is flawed by its conversion of a substantial amount ofreactant into unwanted high boiling compounds, as well as the need tooperate at relatively high pressures. U.S. Pat. No. 4,405,821 disclosesanother similar process involving carrying out the reaction in thepresence of a glycol aldehyde yield enhancing phosphine-oxide. A severeproblem associated with several of the just cited processes is that theyinvolve the addition of a base which catalyzes side reactions of thereactants and forms products through the unwanted mechanism of aldolcondensation. For example, condensation products such as glyceraldehyde,1,3 dihydroxypropanone, erythrose, and 1,3 trihydroxybutanone, as wellas C₅ and C₆ byproducts have been detected in selectivities of 30 % andmore at high conversions, and have thus rendered any commercial processimpractical.

Another serious problem to be overcome is that the particularlypreferred rhodium-phosphine-amide catalysts disclosed in parentcopending U.S. Application Ser. No. 508,704, as well as the earliestprior art catalytic systems which are active in the formaldehydehydroformylation to glycol aldehyde, are ineffective in catalyzing thesubsequent hydrogenation of glycol aldehyde to ethylene glycol.Furthermore, it has been found that the preferredrhodium-phosphine-amides disclosed in Ser. No. 508,704 also have atendency to migrate into the glycol aldehyde product phase duringextraction, and it is essential, both from the standpoint of saving theexpensive metal catalyst and also for prolonging the activity of thecatalyst, to prevent this migration from occurring. In copending U.S.patent application Ser. No. 597,003, now U.S. Pat. No. 4,496,781, thedisclosure of which is incorporated by reference, an improved processhas been developed using the particularly preferred lipophilicphosphine-amide catalysts disclosed in Ser. No. 596,994 to extract theglycol aldehyde into an aqueous phase, from which it can be purified andthen hydrogenated to the desired ethylene glycol.

A still additional flaw is the necessity for both the prior artcatalytic systems, as well as applicant's phosphine-amide class ofcatalysts, to operate at extremely high pressures, in order to obtain adesirable reaction rate, e.g., about 3800 psi is typical for a mostpreferred mode of operation, consequently requiring a substantialinvestment for suitable apparatus. It would be a significant improvementif a catalytic process could be developed which operates effectively atsignificantly lower pressures; such a process and the attendantfinancial savings could make the difference between a major commercialsuccess and a failure.

Accordingly, it is an object of this invention to provide an improvedprocess for the hydroformylation of formaldehyde to glycol aldehyde andits subsequent hydrogenation to ethylene glycol, which has highconversions of formaldehyde and fast rates at relatively low pressures,using a variety of organic solvents, from the reaction of formaldehyde,carbon monoxide and hydrogen feedstocks.

It is another object of this invention to provide a process wherein theglycol aldehyde and the transition metalphosphine-amide and/orphosphine-amine catalysts can be easily separated and extracted orrecycled from the reaction product mixture in an effective industrialoperation.

It is still another object of this invention to develop ahydroformylation catalyst which can effect formaldehyde hydroformylationwith a commercially available formaldehyde feed (i.e., 37% formaldehydein water or 50% in methanol).

It is still another object of this invention to provide a catalyst forthe hydroformylation of formaldehyde which is capable of being recycleda substantial number of times without experiencing a significant loss incatalytic activity.

SUMMARY OF THE INVENTION

Accordingly, the invention provides for a first improved process andaccompanying catalyst for the production of glycol aldehyde, comprisingcontacting formaldehyde, carbon monoxide and hydrogen with an effectivepolar organic solvent, or, a mixture of polar-non polar organicsolvents, in a reaction zone, under suitable superatmospheric pressure,e.g., preferably from about 140 to 280 atm., and elevated temperatureconditions, in the presence of a rhodium, cobalt, orruthenium-containing catalyst, most preferably rhodium, includingmixtures thereof; the catalyst further including a carbon monoxideligand and a phosphine ligand incorporating therein an ancillarytertiary amide group. The presence of the phosphine-amide ligand in theresultant metal carbonyl complex permits the formation of complexeshaving the formula, MX_(x) (CO)_(y) [P(R₁)₂ R₂ C(O)--NR₃ R₄ ]_(z)wherein M is an element selected from the group of rhodium, cobalt,ruthenium and mixtures thereof; X is an anion, preferably a halide, apseudohalide, a hydride or a deprotonated strong carboxylic acid; P isphosphorous; R₁ is an aromatic, aliphatic or mixed group of 1-20 carbonatoms, preferably aromatic; R₂ is an optional organo group containing,if present, from 1 to 20 carbon atoms of alkyl, aryl or alkaryl nature,which may include oxygen, nitrogen or sulfur atoms, which atoms may bedirectly bonded to the amide {C(O)N}carbon, or nitrogen; R₃ and R₄ areeach aliphatic, aromatic or mixed groups containing from 1 to 100 carbonatoms; the resultant compound being characterized by the absence ofhydrogen on the amide nitrogen atom and the additional limitation thatif R₂ is bonded to the amide nitrogen, then either R₃ or R₄ is bonded tothe amide carbon; x ranges from 0 to 3, y ranges from 1 to 5, and zranges from 1 to 4. Surprisingly, it has been found that the usage of amember of a preferred class of lipophilic phosphine-amides havingstructures as indicated above, wherein at least one of R₃ and R₄ rangefrom about 10 to 100 carbons, and, most preferably, the compound PPh₂CH₂ CH.sub. 2 C(O)N(CH₃)[(CH₂)₁₇ CH₃ ] (Ph is phenyl) and the like areparticularly active catalysts for the hydroformylation reaction, whichalso displays a substantial solubility in non polar organic solvents,thereby greatly improving subsequent product and catalyst separation andrecycling operations. The usage of this particular class of complexespermits a wide variety of desirable organic polar compounds such asnitriles, ketones, ethers and the like, as well as mixtures, to beeffective solvents in the process, and further permits the utilizationof the preferred process scheme set forth in Ser. No. 597,003, now U.S.Pat. No. 4,496,781, thereby producing high conversions and selectivitiesto glycol aldehyde and further assisting in an effective productrecovery and a catalyst purification and recycling cycle.

The invention further provides for a second improved process andaccompanying catalyst for the production of glycol aldehyde, comprisingcontacting formaldehyde, carbon monoxide and hydrogen with an effectivepolar organic solvent, or, a mixture of polar-non polar organicsolvents, in a reaction zone, the reaction proceeding at a suitable rateunder preferably, suitable lower, i.e., as low as about 1000 to 3000psia, superatmospheric pressures and elevated temperature conditions, inthe presence of a rhodium, cobalt, or ruthenium-containing catalyst,most preferably rhodium, including mixtures thereof; the catalystfurther including carbon monoxide, a phosphine ligand incorporatingtherein an ancillary amine ligand, and, preferably, a stoichiometricexcess of a triaryl phosphine ligand. The presence of thephosphine-amine ligand in the resultant metal carbonyl complex permitsthe formation of complexes having the formula, MX_(w) (CO)_(x) [P(R₁)₂R₂ --NR₃ R₄ ]_(y) [P(R₅)₃ ]_(z), wherein M is an element selected fromthe group of rhodium, cobalt, ruthenium and mixtures thereof, peferablyrhodium; X is an anion, preferably a halide, a pseudohalide, a hydrideor a deprotonated strong carboxylic acid; P is phosphorous; R₁ is anaromatic, aliphatic or mixed group of 1 to 20 carbon atoms, preferablyaromatic; R₂ is an organo group containing from 1 to 20 carbon atoms ofalkyl, aryl or alkaryl nature which may include oxygen, nitrogen and/orsulfur atoms; R₃ and R₄ can each be hydrogen or aliphatic, aromatic ormixed groups, the non hydrogen groups containing from 1 to 100 carbonatoms; R₅ is an aliphatic, aromatic or mixed group containing from 1 to100, preferably 6 to 50 carbon atoms; w ranges from 0 to 3, x from 1 to5, y from 1 to 4 and z from 0 to 3. Surprisingly, the usage of such anovel class of phosphine-amines, either in or out of the presence oftriaryl phosphines, has permitted the usage of substantially lowerpressures, e.g., as low as about 1000 to 3000 psia, in the preferredoperating system while still permitting sufficiently high reactionrates, reactant conversions and product selectivities. The processproduces a reduced amount of unwanted condensation products, even whenin the presence of the basic phosphine-amines present in the system, inthe presence of significant amounts of water, and the catalyst system issurprisingly compatible in the presence of excess amounts oftriarylphosphine, in sharp contrast to most prior art systems.

The invention further provides for a third class of catalytic compoundsinvolving a variety of mixtures of elements from the first process,i.e., phosphine-amides, mixed with elements from the second process,i.e., phosphine-amines either in or out of the presence of an excessamount of triarylphosphines, in a wide variety of organic solvents.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention can be accomplished by either (1)contacting formaldehyde, carbon monoxide, and hydrogen with an effectivepolar organic solvent, or, a mixture of polar-non polar organicsolvents, in the presence of a transition metal, e.g., rhodium,ruthenium or cobalt-containing, catalyst including various mixturesthereof; the catalyst complex further including a carbon monoxide ligandand also having as a substituent a phosphine ligand incorporating anancillary tertiary amide group, in the presence of elevated temperaturesand superatmospheric pressures, that is, under general conditionssuitable for hydroformylation with the particular catalyst chosen. Mostpreferably, the hydroformylation process follows the scheme set forth incopending U.S. patent application Ser. No. 597,003 now U.S. Pat. No.4,496,781, which describes a method of hydroformylation which can alsoeffectively recover and recycle a still active catalyst without thedrawbacks of the prior art processes. A high boiling non polar organicsolvent which is immiscible with glycol aldehyde, such as toluene orxylene, is added to the reaction zone together with an effective lowboiling polar organic solvent, such as acetonitrile, the latter being aparticularly effective hydroformylation solvent. The resulting effluentis then separated to remove the low boiling polar solvent, while theremaining non polar high boiling solvent, together with the glycolaldehyde product, separates into two phases. Due to the difference insolubility of the solvent and glycol aldehyde, the glycol aldehyde isprecipitated out of solution while the rhodium catalyst remains in thesolvent or xylene phase. The two phases are then separated, with thexylene phase which contains the catalyst recycled back to thehydroformylation reactor and the glycol aldehyde product, which issubstantially free from the rhodium catalyst, is separated and laterhydrogenated. Such a process, however, requires a catalyst which is botheffective in the hydroformylation reaction, while also being easilyseparable and capable of retaining its catalytic activity afterprocessing. This requirement is a particularly troublesome point, sinceduring product separation the preferred rhodium-phosphine-amides havetended to migrate into the glycol aldehyde layer, thereby causing asubstantial loss of expensive catalyst, as well as a substantialdecrease in catalytic activity on recycling. Although in the prior artliterature the difficulties of the product separating operation areeither ignored or allegedly solved by the particular solvent systemdisclosed, it is believed that there are to date no commercialembodiments of these processes, and that the inability of the art todevelop an effective separation process is the major reason.

The hydroformylation process can also be accomplished by (2) contactingformaldehyde, carbon monoxide, and hydrogen with an effective polarorganic solvent, or, a mixture of polar-non polar organic solvents, inthe presence of a suitable transition metal, e.g., a rhodium, rutheniumor cobalt containing catalyst including various mixtures thereof, thecatalyst complex further including a carbon monoxide ligand, a phosphineligand incorporating an ancillary amine group and preferably, in thepresence of a stoichiometric excess of a triaryl phosphine ligand, inthe presence of elevated temperatures and superatmospheric pressures,that is, under general conditions suitable for hydroformylation with theparticular catalyst chosen. The hydroformylation can also beaccomplished by utilizing a wide variety of mixtures of member(s) ofeach of the two classes of catalytic compositions.

One problem with this reaction as practiced by the prior art has beenthat glycol aldehyde tends to form acetals, a reaction typical ofaldehydes. Since there is a primary alcohol group present in themolecule, this compound can easily form semi-acetals and acetals withitself in the form of, for example, linear and cyclic-acetals such asare represented by the following structures: ##STR1##

In addition, glycol aldehyde also forms acetals and semi-acetals withmethanol, and if present, ethylene glycol. Acetals are resistant tohydrogenation, as well as possessing high boiling points, and thereforecan present a difficult process impediment to ethylene glycol formation.Two further problems faced by the reaction system are that the glycolaldehyde product can react with either formaldehyde or with itselfthrough the mechanism of aldol condensation, and the reaction can alsobe inhibited by the product glycol aldehyde which can form bidentateligands with the coordination metal, i.e., rhodium, and thereby displacea monodentate phosphine ligand.

A particularly broad first class of metal complexes or precursors whichhave been found to be suitable as catalysts for the hydroformylationreaction and the subsequent separation and recycle can be represented bythe equation: MX_(x) (CO)_(y) [P(R₁)₂ R₂ C(O)--NR₃ R₄ ]_(z) wherein M isan element selected from the group of rhodium, cobalt and ruthenium,including mixtures thereof, X is an anion, preferably a halide, apseudohalide, a hydride or a deprotonated strong carboxylic acid, P isphosphorous, R₁ is an aliphatic, aromatic, or a mixture thereof group of1-20 carbon atoms attached directly to the phosphorous atom, R₂ is anoptional organo group containing, if present, from 1 to 20 carbon atomsof alkyl, aryl or alkaryl nature, and may include such atoms as oxygen,nitrogen, sulfur and the like, which atoms may also be directly attachedto the amide carbon or nitrogen; R₃ and R₄ are each aliphatic, aromaticor a mixture thereof group of 1 to 100 carbon atoms, and, preferably, atleast one of the R₃ and R₄ moieties will be an aliphatic grouppossessing about 10 to about 100 carbon atoms; the resultant amidemoiety being characterized by the absence of hydrogen on the amidenitrogen and the additional limitation that if R₂ is bonded to the amidenitrogen, then either R₃ or R₄ is bonded to the amide carbon; x rangesfrom 0 to 3, y ranges from 1 to 5, and z from 1 to 4. Most preferably,the incorporation of a lipophilic phosphine-amide having the structurePPh₂ CH₂ CH₂ C--(O)N(CH₃)[(CH₂)₁₇ CH₃ ], or similar thereto, inconjunction with a rhodium complex, both forms a particularly activecatalyst for the hydroformylation reaction and also is particularlysoluble in non polar organic solvents, thereby greatly facilitatingsubsequent product separation operations. The synthesis of such apreferred class of catalysts has involved attaching an "organic tail"into the ligand, thus making the ligand lipophilic, that is, a moleculewhich has a substantial solubility in a non polar medium even thoughpossessing a substantially polar moiety within its structure. Such aconcept is believed novel to carbonylation chemistry, and isaccomplished by having either one or both R₃ and R₄ groups comprise along aliphatic chain, preferably from at least about 10 to about 100carbons in length. Surprisingly, the addition of such a tail to thephosphine-amide has made possible an effective catalyst separationprocess in which substantially all of the expensive phosphine-amidecatalyst is prevented from migrating into the glycol aldehyde phase; infact, less than 100 ppm of rhodium tend to migrate to the glycolaldehyde phase in the preferred process of the invention, as contrastedwith about 1000 to 1500 ppm, using the preferred phosphine-amidesdisclosed in Ser. No. 508,704.

A second particularly broad class of metal complexes of precursors whichhave been found to be suitable as catalysts for the hydroformylationreaction can be represented by the equation: MX_(w) (CO)_(x) [P(R₁)₂ R₂--NR₃ R₄ ]_(y) [P(R₅)₃ ]_(z) wherein M is an element selected from thegroup of rhodium, cobalt and ruthenium, including mixtures thereof, X isan anion which can be a halide, a pseudohalide, a hydride or adeprotonated strong carboxylic acid, P is phosphorous, R₁ is analiphatic, aromatic, or a mixture thereof group of 1 to 20 carbon atomsattached directly to the phosphorous atom, R₂ is an organo groupcontaining from 1 to 20 carbon atoms of alkyl, aryl or alkaryl nature,and may include such atoms as oxygen, nitrogen, sulfur and the like;either or both of R₃ and R₄ can be hydrogen, or aliphatic, aromatic or amixture thereof moieties of 1 to 100 carbon atoms; R₅ is an aliphatic,aromatic or mixed group containing from 1 to 100 carbon atoms; w rangesfrom 0 to 3, x ranges from 1 to 5, y from 1 to 4 and z from 0 to 3. Mostpreferably, phosphine-amines having the structure PPh₂ (CH₂)₃ N(CH₃)₂,PPh₂ (CH₂)₄ N(CH₃)₂, and ##STR2## (Ph represents phenyl), in conjunctionwith a rhodium complex, are active catalysts for the hydroformylationreaction. The pKa of the accompanying amine moiety, preferably presentin a stoichiometric excess, must also be greater than or equal to 1.0.It is most preferred to use amines possessing a pKa ranging from about3.0 to 12.5.

The anion element X in either of the aforementioned complexes can be ahydride, a halide such as chloride, bromide, iodide or fluoride, as wellas pseudohalides which exhibit halide like properties in formingcoordinate compounds and the like, including substituents such as NCS⁻,NCO⁻, CN⁻, NCSe⁻, N₃ ⁻, ##STR3## and the like, or a deprotonated strongcarboxylic or sulfonic acid substituents such as trifluoroacetate,trifluoromethanesulfonate, methanesulfonate, toluene-sulfonate and thelike. The preferred anion containing moieties are chloride,trifluoroacetate and hydride. Alternatively, an anion rhodium speciescan be generated in which no anionic element X is present.

The R₁ group present in the phosphine-amide, or first complex, in thebroadest embodiment represents either an alkyl, an aryl group or amixture thereof, the alkyl group containing from 1-20 carbon atoms, withthe suitable aryl moieties being phenyl and substituted phenyls, otherpolyaromatic and substituted polyaromatics and the like. When cobalt isthe coordinating metal ligand of choice, it is preferred to use alkylsubstituted phosphines, whereas when rhodium or ruthenium is the chosenmetal it is preferred to have R₁ be phenyl or another aryl moiety.

The R₁ group present in the phosphine-amine, or second complex, in thebroadest embodiment represents either an alkyl, an aryl or an alkyl-arylgroup thereof, the group containing from 1 to 20 carbon atoms,preferably about 6 to 10 carbons of aryl character, with the suitablearyl moieties being phenyl and substituted phenyls, other polyaromatics,substituted polyaromatics and the like.

The R₂ group, in the first complex, in the broadest embodiment,represents, if present, an organo group containing from 1 to 20 carbonatoms, preferably from 1 to 2 carbon atoms, and is preferably free fromacetylenic unsaturation. R₂ can be saturated aliphatic, alkenyl, oraromatic and can be either a hydrocarbyl group containing only carbonand hydrogen, or, a substituted hydrocarbyl group containing in additionto atoms of carbon and hydrogen additional atoms such as nitrogen,oxygen, sulfur and the halogens, which additional atoms can also bepresent in various groups such as alkoxy, aryloxy, carboalkoxy,alkanoyloxy, halo, trihalomethyl, cyano, sulfonyalkyl and the likegroups which contain no active hydrogen atoms. Most preferably, R₂ iscomprised of aliphatic groups containing only carbon and hydrogen.

The R₂ group in the second complex in the broadest embodiment representsan alkyl, an aryl, or an alkaryl group thereof, the group containingfrom about 1 to 20 carbon atoms, preferably from 2 to 4 carbons, and canbe saturated aliphatic, alkenyl, or aromatic. R₂ can be either ahydrocarbyl group containing only carbon and hydrogen, or, a substitutedhydrocarbyl group containing in addition to atoms of carbon and hydrogenadditional atoms such as nitrogen, oxygen, sulfur and the halogens,which additional atoms can also be present in a variety of groupsincluding alkoxy, aryloxy, carboalkoxy, alkanoyloxy, halo,trihalomethyl, cyano, sulfonylalkyl and the like groups which contain noactive hydrogen atoms. Most preferably, R₂ is comprised of aliphaticgroups containing only carbon and hydrogen.

Illustrative of suitable R₁ and R₂ moieties for both classes of catalystcomplexes are hydrocarbon alkyls such as methyl, ethyl, propyl,isobutyl, cyclohexyl, and cyclopentyl; hydrocarbon alkenyl moieties suchas butenyl, hexenyl, cyclohexenyl; alkyl or alkenyl moieties havingaromatic substituents such as benzyl, phenylcyclohexyl andphenylbutenyl; and substituted-hydrocarbyl moieties such as4-bromohexyl, 4-carbethoxybutyl, 3-cyanopropyl, chlorocyclohexyl andacetoxybutenyl. Aromatic moieties are exemplified by hydrocarbylaromatic groups such as phenyl, tolyl, xylyl, p-ethylphenyl, andsubstituted hydrocarbyl aromatic groups such as p-methoxyphenyl,m-chlorophenyl, m-trifluoromethylphenyl, p-propoxyphenyl, p-cyanophenyl,o-acetoxyphenyl and m-methyl-sulfonylphenyl.

R₃ and R₄ in the first complex represents organo groups of 1 to 100carbon atoms, preferably at least one being of 10 to 100 carbons, andcan be either aromatic, aryalkyl, or preferably, aliphatic in nature.Suitable groups are the saturated aliphatics of both a cyclic or alinear makeup, aromatics, preferably mononuclear aromatics, and thelike. It is most preferred that R₃ and R₄ be comprised of only carbonand hydrogen atoms. It is also most preferred that the amide moiety inthe resultant phosphine ligand be characterized by the absence ofhydrogen on the amide nitrogen atom; e.g., tertiary amide groups aremost preferred. In the case where R₂ is bonded to the nitrogen, insteadof the amide carbon, then either R₃ or R₄ is bonded to the amide carbon.A second organophosphine group can also be incorporated into one or bothof the R₃ or R₄ groups.

Either or both R₃ and R₄ in the second complex can represent hydrogen,or organo groups of 1 to 100 carbon atoms, and preferably at leasteither R₃ or R₄ ranges from 1 to 20 carbons, and can be either aromatic,mixed, or preferably, aliphatic in nature. Suitable groups are thesaturated aliphatics of both a cyclic or a linear makeup, aromatics,preferably mononuclear aromatics, and the like. It is also mostpreferred that R₃ and R₄ be comprised of only carbon and hydrogen atoms.Tertiary amines are preferred for incorporation into the catalyst,although primary and secondary amine ligands are also suitable for use.A second organophosphine group can also be incorporated into one or bothof the R₃ or R₄ groups.

The resulting phosphine-amine compositions employed in thehydroformylation process of this invention are basic, i.e., basic usedherein representing that the amine composition has a pH in watersolution which is higher than the pH of such reactants or solvents. Theclass of basic phosphine-amines used in the process must have a pKa ofat least 1.0, and preferably in the range of about 3.0 to 12.5 sincesuch a subclass of amines generally provide improved reaction rates.

The phosphine-amides and phosphine-amines herein disclosed can bepresent in widely varying amounts with a tendency to use less of thephosphine-amine or amide as its basic character increases. Thephosphine-amine or amide to coordination metal, e.g., rhodium, ratio canrange from about 4/1 to 1/1, most preferably about 3/1 to 2/1, while thetriarylphosphine to rhodium ratio in the phosphine-amine system canrange from about 100/1 to 5/1, most preferably about 50/1 to 10/1.

R₅ represents, in the broadest embodiment, either an alkyl, an aryl oran alkaryl group thereof, with R ranging from 1 to 100 carbon atoms,preferably about 6 to 50 carbons, with the preferred aryl moieties beingphenyl, m-trifluorophenyl, p-chlorophenyl, p-trifluoromethylphenyl,p-cyanophenyl and p-nitrophenyl. It is preferred to have an electronwithdrawing group on the phenyl, although not necessarily in the paraposition.

The transition metal compound suitable for use in the reaction isselected from rhodium, cobalt or ruthenium, as well as various mixturesthereof, and most preferably is a rhodium compound, complex, or salt.The metal compound may be deposited or affixed to a solid support suchas a molecular sieve, zeolite, activated carbon, alumina, silica, an ionexchange resin, an organic polymeric resin, or as an insoluble rhodiumoxide, but most preferably is used as a homogeneous complex in solution.

A representative phosphine-amide ligand can be synthesized through amodification of the method disclosed by Meek et al, J.Chem.Soc.(Dalton), 1011, 1975, in which a phosphorous hydrogen bond cleanly addsto the carbon-carbon double bonds of vinyl derivatives in the presenceof free radicals such as 2,2'-azobis(2-methyl-propionitrile) (AIBN),e.g.: ##STR4## In this case the resulting phosphine exists as a whitesolid at room temperature. The phosphine-amide can also be synthesizedby other routes, such as by photochemical initiation instead of radicalinitiators, or by amination of a phosphine ester.

The synthesis of the preferred class of phosphine-amide ligands,particularly the most preferred species PPh₂ CH₂ CH₂ -C(O)N(CH₃)[(CH₂)₁₇CH₃ ], is preferably accomplished by the amidolysis of PPh₂ CH₂ CH₂C(O)OC₂ H₅ by N(H)(CH₃)[(CH₂)₁₇ CH₃ ] using sodium methoxide as acatalyst. A temperature of about 50° C. to 150° C. for about 1 to 50hours and a 1 to 1 to a 2 to 1 phosphine to amine ratio have been foundto be satisfactory.

A representative phosphine-amine ligand can be synthesized by thelithium aluminum hydride reduction of the respective phosphine-amide,e.g., ##STR5## The phosphine-amine can also be synthesized by otherroutes, such as by metathesis, e.g.:

    LiPPh.sub.2 +ClCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 →PPh.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 +LiCl

Such a route is outlined by McEwen, et al., J.A.C.S., 102 (8);p2746(1980).

The major product of the hydroformylation reaction is glycol aldehyde,with the major byproduct being methanol. The precise manner ofcontacting the reactants is not critical, as any of the variousprocedures known in the art for this type of reaction can be used solong as there is suitable efficient gas-liquid contact. Thus, forexample, the process may be carried out by contacting a solution offormaldehyde together with the particular catalyst and solvent and amixture of carbon monoxide and hydrogen at the selected condition.Alternatively, the solution of formaldehyde may be passed over andthrough the catalyst in a trickle phase under a mixture of carbonmonoxide and hydrogen at the selected conditions of temperature andpressure. It will, of course, be recognized that the illustratedreactants are capable of undergoing other reactions besides the primaryone, and that, depending upon the particular conditions and specificcatalyst and solvent chosen, there will be concomitant production ofother products in variable amounts, particularly methanol. However, theconditions in the instant process are most preferably regulated so as togive high selectivity to the desired glycol aldehyde.

A suitable source of formaldehyde for the reaction, using the firstcomplex, can be any one of those known in the art, includingparaformaldehyde, methylal, formalin solutions, polyoxymethylenes andthe like. Of these, paraformaldehyde is preferred and maximum yieldshave been obtained from its use.

A suitable source of formaldehyde using the second complex can also beany one of these known in the art, including paraformaldehyde, methylal,formalin solutions, polyoxymethylenes and the like. As can be seen inthe accompanying examples, a major advantage of the process, resultingfrom the use of the second complex over prior art systems such as thatdisclosed in U.S. Pat. No. 4,405,814 is that substantial activity hasbeen found even in the presence of aqeuous or methanolic solutions offormaldehyde, e.g., commercially available 37% formaldehyde and thelike, which can lead to very substantial economic benefits, as theresulting reaction effluent forms only small amounts of glyceraldehydeand traces of other C₃₋₅ condensation products. Also, a lesser amount ofglyceraldehyde and other C₃ -C₅ condensation products are formed in theabsence of water as compared to the resultant system formed by theaddition of the basic amines in U.S. Pat. No. 4,405,814. Anotheradvantage of the process is its compatibility in the presence of excessamounts of triarylphosphines and other similar ligands. Rhodium(I) ismuch more stable to recycle in the presence of excess phosphine ligands,but these ligands, unfortunately, usually slow the rate ofhydroformylation. In this system, however, the hydroformylation reactionrate is substantially unaffected.

While carbon monoxide and hydrogen react in a stoichiometric one-to-oneratio, it is not necessary to have them present in such a ratio toundertake the reaction. As indicated above, the reactant should beemployed at a high enough pressure so as to provide a desirable reactionrate. Carbon monoxide also stabilizes rhodium and other transitionmetals to reduction by formaldehyde to the zero valent state. The carbonmonoxide and hydrogen reactants may conveniently be supplied in about aone-to-one ratio, on a mole basis, such as can be obtained fromsynthesis gas and the like; however, they can also be present in widelyvarying and variable ranges, such as having mole ratios from about 5 to95 to 95 to 5. Excellent yields can be obtained when operating at carbonmonoxide to hydrogen partial pressure ratios as high as 10 to 1. Largeexcesses of hydrogen have a tendency to favor the production of unwantedmethanol.

The catalyst in the first complex can be prepared through a variety oftechniques, e.g., the complex containing carbon monoxide can either bepreformed or formed in situ by the reaction with the transition metal.Several convenient methods for in situ preparation are to contact ametal complex precursor with the phosphine-amide and an acid such astrifluoroacetic acid; to contact a metal carbonyl halide, e.g.,[RhCl(CO)₂ ]₂ with the phosphine-amide; to contact a preformed metalcoordination complex such as Rh(Cl) (CO) (PPh₃)₂ with the desiredphosphine-amide; or to contact the metal carbonyl halide, e.g.,[RhCl(CO)₂ ]₂ with a catalytic amount of base and the phosphine-amide.

Although it is not wished to be bound by theory, the reason for theselectivity of the formaldehyde hydroformylation to glycol aldehyde whenusing the transition metal-phosphine-amide in non amide solvents is mostlikely to be found in the size and resulting stability of the formedchelate ring. Depending on the particular metal used, and, to a lesserextent, the particular phosphine-amide ligand employed, a variety ofdesired bidentate complexes can be created, which complexes apparentlybond with the transition metal at the phosphorous and the amide groupoxygen. For example, the preferred phosphine-amide ligands,N-methyl-N-octadecyl diphenylphosphino-propionamide, PPh₂ CH₂ CH₂ C(O)N(CH₃) [(CH₂)₁₇ CH₃ ], is believed to form a 6-membered ring with rhodiumand is surprisingly active, as well as selective to glycol aldehyde.

A number of suitable non-lipophilic phosphine-amide ligands areexemplified below: ##STR6## PPh₂ OCH₂ C(O)N(CH₃)₂ ; PPh₂ N(CH₃)CH₂C(O)N(CH₃)₂ ; ##STR7## PPh₂ CH₂ CH₂ N(CH₃)C(O)CH₃ ; ##STR8## P(CH₂ CH₂CH₂ CH₃)₂ [CH₂ CH₂ C(O)N(CH₃)₂ ]'

PPh₂ CH₂ CH₂ C(O)N(CH₃) (CH₂ CH₂ CH₂ CH₂ CH₂ CH₂ CH₂ CH₃);

PPh₂ CH₂ C(O)N(CH₃)₂ ; PPh₂ CH₂ N(CH₃)C(O)CH₃

PPh₂ CH₂ CH₂ C(O)N(CH₃)CH₂ PPh₂ ##STR9## PPh₂ CH₂ CH₂ C(O)N(CH₂ Ph) (CH₂CH₃) PPh₂ CH₂ CH₂ C(O)N(Ph) (CH₂ CH₂ CH₂ CH₃) ##STR10## PPh₂ CH₂C(O)N(Ph)₂

A number of preferred suitable lipophilic phosphine-amide ligands areexemplified below: ##STR11## PPh₂ OCH₂ C(O)N(CH₃) (C₁₈ H₃₇) PPh₂N(CH₃)CH₂ C(O)N(CH₃) (C₃₀ H₆₁) ##STR12## PPh₂ CH₂ CH₂ N(C₁₀ H₂₁)C(O)(C₁₀ H₂₁) ##STR13## P(C₄ H₉)₂ [CH₂ CH₂ C(O)N(CH₃)](C₁₈ H₃₇)

PPh₂ CH₂ CH₂ C(O)N(CH₃) (C₅₀ H₁₀₁)

PPh₂ CH₂ C(O)N(CH₃) (C₁₈ H₃₇)

PPh₂ CH₂ N(C₁₀ H₂₁)C(O) (C₂₀ H₄₁)

PPh₂ CH₂ CH₂ C(O)N(C₂₀ H₄₁) (CH₂ Ph) ##STR14## PPh₂ CH₂ CH₂ C(O)N(CH₂Ph) (C₂₀ H₄₁) PPh₂ CH₂ CH₂ C(O)N(Ph) (C₂₀ H₄₁) ##STR15## PPh₂ CH₂C(O)N(Ph) (C₂₀ H₄₁) PPh₂ CH₂ CH₂ C(O) (C₂₀ H₄₁) (C₁₀ H₂₁)

The second class of catalyst complexes can be prepared through a varietyof techniques, e.g., the complex containing carbon monoxide can eitherbe preformed or formed in situ by the reaction with the transitionmetal. Several convenient methods for in situ preparation are:contacting a metal carbonyl halide, e.g., [RhCl(CO)₂ ]₂ with thephosphine-amine and an excess of triarylphosphine ligand, contacting apreformed metal coordination complex such as Rh(Cl(CO) (PPh₃)₂ with thedesired phosphine-amine, or contacting [Rh(Cl) (CO₂ ]₂ with only thephosphine-amine.

Although it is not wished to be bound by theory, the reason for theselectivity of the formaldehyde hydroformylation to glycol aldehyde whenusing the transition metal-phosphine-amine is most likely to be found inthe size and resulting stability of the formed chelate ring. Dependingon the particular metal used, and, to a lesser extent, the particularphosphine-amine ligand employed, a variety of desired bidentatecomplexes can be created, which complexes apparently bond with thetransition metal at the phosphorous and the amine group nitrogen.

A number of suitable phosphine-amine ligands are exemplified below:

PPh₂ OCH₂ CH₂ N(CH₃)₂, PPh₂ OCH₂ CH₂ NH₂ ##STR16## PPh₂ CH₂ CH₂ N(CH₃)(C₂₀ H₄₁), PPh₂ CH₂ CH₂ N(CH₃)CH₂ CH₃ ; PPh₂ CH₂ CH₂ N(CH₃) (H)##STR17## P(CH₂ CH₂ CH₂ CH₃)₂ [CH₂ CH₂ CH₂ N(CH₃)₂ ]

PPh₂ CH₂ CH₂ CH₂ N(CH₃) (CH₁₈ H₃₇) ##STR18## (C₁₈ H₃₇) (CH₃)N CH₂ (C₁₈H₃₇) (CH₃)N P(C₄ H₉)₂ CH₂ CH₂ CH₂ N CH₃ (C₁₈ H₃₇)

PPh₂ CH₂ CH₂ CH₂ N(CH₂ Ph) (C₂₀ H₄₁)

PPh₂ CH₂ CH₂ CH₂ N(CH₃)₂

PPh₂ CH₂ CH₂ N(Ph) (CH₃)

PPh₂ (CH₂)₄ N(CH₃)₂ ; PPh₂ (CH₂)₄ NH₂

PPh₂ (CH₂)₄ N(CH₃) (C₂₀ H₄₁) ##STR19##

The usage of this novel class of catalyst complexes has surprisinglypermitted the use of a great many more different solvents than haveheretofore been found effective in such reactions. Although certainnon-polar solvents, as well as mixtures, have proven to be operable, theuse of polar solvents, and particularly organic polar solvents has beenfound to be generally preferred. Particularly preferred as solvents arenitriles, such as acetonitrile, benzonitrile, propionitrile and thelike; cyclic ethers such as tetrahydrofuran, dioxane andtetrahydropyran; ethers such as diethyl ether, 1,2-dimethoxybenzene,alkyl ethers of alkylene glycols and polyalkylene glycols, e.g., methylethers of ethylene glycol, propylene glycol and di-, tri-, andtetraethylene glycols; alkyl sulfones and sulfoxides such as sulfolaneand dimethylsulfoxide, ketones such as acetone, methyl isobutyl ketone,and cyclohexanone; esters such as ethyl acetate, ethyl propionate andmethyl laurate; lactones of organic carboxylic acids such asbutyrolactone and valerolactone, tertiary amides such asN,N-dibutylformamide and N,N dimethylacetamide, organic acids such asacetic acid, propionic acid and caproic acid, and alkanols, such asmethanol, ethanol, propanol, 2-ethylhexanol and the like, as well as awide variety of mixtures thereof. Non polar organic solvents such asbenzene, toluene and the like are also operable if used in mixtures withpolar organics. The selected solvent should preferably be liquid underthe reaction conditions.

The usage of the most preferred class of lipophilic complexes for thefirst complex as catalysts has permitted the use of a solvent mixturewhich is both particularly adaptable for hydroformylation and also forproduct and catalyst separation. Suitable solvents for the mostpreferred embodiment of the process are selected from the class oforganic polar, low boiling solvents and the class of organic non polar,high boiling solvents, which combine to form a mixture containing atleast one element of each group, and are disclosed in copendingapplication Ser. No. 597,003, now U.S. Pat. No. 4,496,781. The preferredsolvent mixture is an acetonitrile-xylene-diethyl ether mixture.

An improvement resulting from the catalyst complexes described herein isthat in solution the phosphine-amides form bidentate ligands which aremore resistant to displacement by glycol aldehyde than the prior artmonodentate phosphines. This means that, in sharp contrast to prior artsystems, the glycol aldehyde product does not have to be removed fromthe reaction media shortly after its formation so as to insure thestability of the catalyst. Such properties are extremely helpful inoptimizing product yield and facilitating product and catalystseparation. The reaction can also be carried out at higherconcentrations of formaldehyde without any harmful side reactions.

A particularly surprising and useful property of the phosphine-aminecatalyst system is the ability to obtain commercially satisfactoryreaction rates at about 1000 to 3000 psia, typically at about 2500 psiaCO:H₂, in sharp contrast to the system pressures of 3800 psia requiredboth in the phosphine-amide and also in other prior art systems. Such animprovement permits a substantial reduction in apparatus costs.Additionally, these catalyst complexes are also effective in thepresence of a wide variety of solvents, in contrast to prior artsystems, and also form a substantially reduced number of unwanted highboiling byproducts.

As in other processes of this kind, the reaction can be conducted ineither a batch, semi-continuous or continuous mode of operation. It isnaturally desirable to construct the reactor from materials which canwithstand the operating temperatures and pressures required, whilekeeping the internal surfaces of the reactor substantially inert.Standard equipment known to permit control of the reaction, such as heatexchangers and the like, may be used. The reactor should be providedwith an adequate means for agitating the reaction mixture; such mixingcan be induced by vibration, shaking, stirring, oscillation, and similartype methods.

The reaction resulting in the production of glycol aldehyde, togetherwith lesser amounts of methanol, is usually complete within a period ofabout 2-3 hours, in the case of the phosphine-amide catalyst complexsystem, and within about 1 hour for the phosphine-amines, althoughreaction time is not a critical parameter of the process, and longer orshorter times can be effectively employed. Substantially higherconcentrations of reactants than previously utilized are preferred.

The amount of catalyst employed in the hydroformylation reaction processhas not been found to be critical and can vary considerably. At least acatalytically effective amount of catalyst should be present, andpreferably a sufficient amount of catalyst which is effective to providea reasonable reaction rate. As little as 10⁻⁵ moles of catalyst perliter of reaction medium can suffice, while amounts in excess of 10⁻¹moles do not appear to materially affect the rate of reaction. For mostpurposes, an effective preferred amount of catalyst falls in the rangeof from about 10⁻² to about 10⁻³ moles per liter.

The precise reaction conditions chosen are not particularly critical inthat a wide range of elevated temperatures and superatmosphericpressures are operable. The preferred temperature range in the case ofthe phosphine-amide complexes should be at least about 50° C. and canrange up to about 150° C. and even higher, although no substantialbenefits are realized at this temperature level. Most preferably, theoperating temperatures will range from about 90° C. to about 130° C. Thesuperatmospheric pressures for this system should be at least about 70atmospheres and can range, in theory, to almost any pressure attainablewith available production apparatus. Most preferably, operatingpressures should fall in the range of about 140 to about 280atmospheres, particularly when operating in the preferred aforementionedtemperature range.

The preferred temperature range in the case of the phosphine-aminesystem should be at least about 50° C. and can range up to about 150° C.and even higher, although no substantial benefits are realized at thistemperature level. Most preferably, the operating temperatures willrange from about 90° to about 120° C. The superatmospheric pressuresshould be at least about 50 atmospheres and can range, in theory, toalmost any pressure attainable with available production apparatus. Mostpreferably, operating pressures should fall in the range of about 70 toabout 200 atmospheres, particularly when operating in the preferredaforementioned temperature range.

The following examples are provided to illustrate the invention inaccordance with the principles of this invention but are not construedas limiting the invention in any way except as indicated by the appendedclaims. In the examples, selectivity is defined as mmoles of productdivided by moles of reacted formaldehyde times 100.

EXAMPLES

The phosphine-amides were prepared by the following general methods:

Preparation of N,N-dimethyl-3-diphenylphosphinopropionamide [PPh₂ CH₂CH₂ C(O)N(CH₃)₂ ]

A 100 ml 3-necked round bottomed flask was preheated to 100° C. under anitrogen atmosphere and 7.14 g diphenylphosphine (38.4 mmole) from Alfa,0.15 g 2,2'-azobis (2-methylpropionitrile) from Aldrich, and 3.78 gdimethylacrylamide (38.2 mmole) from Polysciences were added in thestated sequence. The reaction mixture was maintained at 100° C. under anitrogen atmosphere for 45 minutes and then evacuated (1 mm) for 24hours at 100° C. The resulting oil was then cooled in the refrigeratorfor several hours until it solidified to a white solid. It was thenwashed with a 9:1 pentane:toluene mixture so as to free the excessdiphenylphosphine.

The infrared spectra disclosed a strong γ (CO) band at 1650 cm⁻¹. The ¹H NMR showed a multiplet at 2.2-2.5δ with a relative area of 4 assignedto the CH₂ CH₂ C(O) group; a doublet at 2.83δ (3 Hz) of relative area 6assigned to the N(CH₃)₂ group; and a multiplet at 7.1-8.3δ of relativearea of 10 assigned to the P(C₆ H₅)₂ group.

The elemental analysis was the following: calculated (found); C, 71.58(70.95); H, 7.02 (7.03); N, 4.91 (4.05); P, 10.87 (10.75). Product Yieldwas 71%

Preparation of N-methyl-N-(2-diphenylphosphinoethyl) acetamide [PPh₂ CH₂CH₂ N(CH₃)C(O)CH₃ ]

A 100 ml 3-necked round bottomed flask was heated to 100° C. under anitrogen atmosphere and 7.14 g diphenyl-phosphine (38.4 mmole), 0.15 g2,2'-azobis (2-methylpropionitrile), and 3.77 g N-vinyl-N-methylacetamide (38.1 mmole) from Polysciences were added in the statedsequence. The reaction was maintained at 100° C. for 45 minutes under anitrogen atmosphere and then evacuated (1 mm) for 24 hours at 100° C. Aviscuous oil resulted whose infrared spectrum displayed a strong γ (CO)band at 1645 cm⁻¹ and a small γ (P-H) band at 2300 cm⁻¹ due to a smallamount of diphenylphosphine impurity. The elemental analysis was thefollowing: calculated (found); C, 71.58 (69.89); H, 7.02 (7.15); N, 4.91(4.57); P, 10.87 (10.97). The yield was 94%.

Preparation of N-(-2-diphenylphosphinoethyl)-2-pyrrolidinone ##STR20##

The cited phosphine-amide was prepared in a similar manner to theearlier two examples by using 14.28 g diphenylphosphine (76.8 mmole),0.30 g 2,2'-azobis (2-methylpropionitrile) and 8.52 gN-vinyl-2-pyrrolidinone (76.8 mmole) from Aldrich. The reactants addedin the stated sequence were stirred at 100° C. for 0.5 hours under anitrogen atmosphere followed by evacuation (1 mm) for 24 hours. Theyield was 96%.

The infrared spectrum disclosed a strong, broad γ (CO) band at 1680 cm⁻¹and a small absorption at 2310 cm⁻¹ due to a small amount of γ (P-H)impurity. The elemental analysis was the following: calculated (found);C, 72.70 (72.68); H, 6.79 (6.73); N, 4.70 (3.49): P, 10.42 (11.60). The¹ H NMR showed a multiplet at 1.6-2.6δ with a relative area of 6assigned at --CH₂ CH₂ C(O)-- and P--CH₂ -- groups, a multiplet at3.2-3.8δ with a relative area of 4 assigned to the two CH₂ --N-groupsand a multiplet at 7.2-8.0δ with a relative area of 11 assigned to theP(C₆ H₅)₂ group. A small amount of diphenylphosphine impurity accountsfor this slightly greater area for the phenyl region. The disappearanceof the multiplet signals of the vinyl protons at 6.9-7.4δ and 4.3-4.7δconfirms the complete disappearance of N-vinylpyrrolidinone.

The following examples illustrate a direct comparison between thephosphine-amides of this invention with triphenylphosphine and in onecase ethyldiphenylphosphine (another alkyldiphenylphosphine) in varioussolvents.

The following examples are provided to illustrate the invention inaccordance with the princples of this invention but are not construed aslimiting the invention in any way except as indicated by the appendedclaims.

EXAMPLE 1

A 300 cc stainless steel autoclave equipped with a stirrer,thermocouple, and cooling coil was charged with 100 g acetonitrile, 3.0g of 95% paraformaldehyde (95 mmole of equivalent formaldehyde), 0.081 gchlorodicarbonylrhodium (I) dimer (0.208 mmole) and 0.364 gN,N-dimethyl-3-diphenylphosphinopropionamide (1.28 mmole), which wassparged with dry nitrogen. The autoclave was sealed and the air wasfurther removed by flushing the autoclave three times with a 1:1 mixtureof carbon monoxide; hydrogen at 100 psi. The autoclave was then chargedwith 1500 psi of the carbon monoxide:hydrogen mixture. The autoclave andits liquid contents were next heated to 130° C. and the final pressureregistered 1900 psi. After three hours, the autoclave was cooled to roomtemperature and the gas was vented. Gas chromatography and high pressureliquid chromatography of the resulting liquid phase disclosed 37 mmoleof formaldehyde remaining (61% conversion) with 35 mmole glycol aldehyde(60% selectivity) and 4.1 mmole of methanol (7.1 % selectivity). Theselectivity is defined as mmoles of product divided by mmoles of reactedformaldehyde times 100 in all examples.

COMPARATIVE EXAMPLE 1

An equimolar concentration of triphenylphosphine was substituted forN,N-dimethyl-3-diphenylphosphinopropionamide, under the identicalconditions of Example 1. Analysis of the liquid phase showed 53 mmole offormaldehyde remaining (44% conversion), with 7.6 mmole of glycolaldehyde and 0.3 mmole of ethylene glycol (20% selectivity) and 8.0mmole of methanol (19% selectivity).

SECOND COMPARATIVE EXAMPLE 1

An equimolar concentration of ethyldiphenylphosphine was substituted forN,N-dimethyl-3-diphenylphosphinopropionamide, under the identicalconditions of Example 1. Analysis of the liquid phase showed 5.5 mmoleformaldehyde remaining (94% conversion) with 0.6 mmole glycol aldehyde(0.7% selectivity) and 1.6 mmole methanol (1.8% selectivity).

EXAMPLE 2

A 125 cc stainless steel Parr bomb equipped with a glass liner and amagnetic stirrer was charged with 25.0 g acetonitrile, 0.75 gparaformaldehyde (23.8 mmole), 0.020 g chlorodicarbonylrhodium (I) dimer(0.058 mmole) and 0.090 g N,N-dimethyl-3-diphenylphosphinopropionamide(0.348 mmole) which had been sparged with nitrogen. The bomb was thencharged with 1500 psi of a 1:1 carbon monoxide; hydrogen mixture, heatedto 130° C. for 3.0 hours, and then cooled to room temperature andvented. Analysis of the liquid contents indicated 9.3 mmole formaldehyderemaining (61% conversion), 11.9 mmole glycol aldehyde (82%selectivity), and 0.2 mmole methanol (1.4% selectivity).

COMPARATIVE EXAMPLE 2

The bomb used in Example 2 was charged and reacted under identicalconditions to those of Example 2 except the catalyst waschlorocarbonylbis(triphenylphosphine)rhodium (I) (0.080 g, 0.116 mmole)in the absence of N,N-dimethyl-3-diphenylphosphinopropionamide asco-catalyst. Analysis of the liquid contents indicated 3.8 mmoleformaldehyde remaining (84% conversion), 0.5 mmole glycol aldehyde (3%selectivity), and 0.4 mmole methanol (2% selectivity).

EXAMPLE 3

The Parr bomb used in Example 2 was charged with 25.0 g acetonitrile,0.75 g paraformaldehyde (23.8 mmole), 0.080 gchlorocarbonylbis(triphenylphosphine)rhodium (I) (0.116 mmole), and0.060 g N,N-dimethyl-3-diphenylphosphinopropionamide (0.232 mmole) whichhad been sparged with nitrogen. The bomb was then charged with 1500 psiof a 1:1 carbon monoxide:hydrogen mixture at room temperature andsubsequently heated to 130° C. for 3.0 hours. After cooling and gasventing, the analysis indicated 7.6 mmoles of formaldehyde remaining(68% conversion), 11.1 mmoles glycol aldehyde (69% selectivity), and 5.0mmoles methanol (31% selectivity).

EXAMPLE 4

The Parr bomb used in Example 2 was run under identical conditions toExample 2 except that an equimolar concentration ofN-methyl-N-(2-diphenylphosphinoethyl)acetamide was substituted forN,N-dimethyl-3-diphenylphosphinopropionamide. Analysis of the liquidcontents indicated 13.4 mmole formaldehyde remaining (44% conversion),5.3 mmole glycol aldehyde (51% selectivity), and 2.1 mmole methanol (20%selectivity).

EXAMPLE 5

The autoclave used in Example 1 was charged with 9.0 g paraformaldehyde(285 mmole), 65.0 g acetonitrile, 30.0 g toluene, 5.0 g diethyl ether,0.301 g N,N-dimethyl-3-diphenylphosphinopropionamide (1.06 mmole), and0.069 g chlorodicarbonylrhodium (I) dimer (0.178 mmole). The autoclavewas charged with 1750 psi carbon monoxide and 450 psi hydrogen at roomtemperature. A 2 liter autoclave reservoir was also charged with thissame carbon monoxide:hydrogen ratio and heated to 250° C. to a totalpressure of 3600 psi. The reactor autoclave was heated to 130° C. for3.0 hours to a total pressure of 3600 psi. When the gas uptake loweredthe gas pressure to 3200 psi, gas was transferred from the reservoirautoclave to the reactor autoclave during the run. Upon completion, theautoclave was cooled to room temperature and slowly vented. Analysis ofthe liquid products revealed 136 mmole formaldehyde remaining (52%conversion), 120 mmole glycol aldehyde (81% selectivity) and 12.9 mmolemethanol (8.7% selectivity).

COMPARATIVE EXAMPLE 5

A comparative example, using an equimolar quantity of triphenylphosphineinstead of N,N-dimethyl-3-diphenylphosphinopropionamide under identicalconditions, resulted in a liquid phase containing 174 mmole formaldehyderemaining (39% conversion), with 27.3 mmole glycol aldehyde (25%selectivity) and 25.2 mmole methanol (23% selectivity).

EXAMPLE 6

The autoclave in Example 5 was charged with 9.0 g paraformaldehyde (285mmole), 65.0 g acetonitrile, 30.0 g toluene, 5.0 g diethyl ether, 0.315g N(-2-diphenylphosphinoethyl)-2-pyrrolidinone (1.06 mmole), and 0.069 gchlorodicarbonylrhodium (I) dimer (0.178 mmole). The autoclave was thencharged with 1750 psi carbon and 450 psi hydrogen at room temperature.The 2 liter autoclave reservoir was also used, as in Example 5. Thereactor autoclave was heated to 130 degrees C. for 3.0 hours. Analysisof the liquid products revealed 137 mmole formaldehyde remaining (52%conversion), 143 mmole glycol aldehyde (97% selectivity) and 3.6 mmolemethanol (2% selectivity).

EXAMPLE 7

The autoclave of Example 5 was charged with 100 g tetraglyme, 9.0 gparaformaldehyde (285 mmole), 0.069 g chlorodicarbonylrhodium (I) dimer(0.177 mole), and 0.301 g N,N-dimethyl-3-diphenylphosphinopropionamide(1.06 mmole). The gas reservoir of Example 5 was again used in the samemanner. The autoclave was charged with 1750 psi carbon monoxide and 450psi hydrogen at room temperature and then heated to 130° C. for 3.0hours to a total pressure of 3600 psi. The autoclave was cooled, vented,and the liquid contents analyzed as 104 mmole formaldehyde remaining(64% conversion), 111 mmole glycol aldehyde and 1.2 mmole ethyleneglycol (62% selectivity), and 14.6 mmole methanol (8.1% selectivity).

COMPARATIVE EXAMPLE 7

A comparative example using an equimolar concentration oftriphenylphosphine instead ofN,N-dimethyl-3-diphenylphosphinopropionamide under identical conditionsresulted in a liquid phase containing 75 mmole formaldehyde remaining(74% conversion), 7.6 mmole glycol aldehyde (3.6% selectivity), and 5.1mmole methanol (2.4% selectivity).

EXAMPLE 8

The autoclave and reservoir of Example 5 were again run under identicalconditions and the charge was identical except that 100 g acetone wasused as the solvent. Analysis of the liquid contents indicated 106 mmoleof formaldehyde remaining (63% conversion), with 145 mmole glycolaldehyde (81% selectivity) and 10.2 mmole methanol (5.7% selectivity).

COMPARATIVE EXAMPLE 8

A comparative example using an equimolar concentration oftriphenylphosphine instead ofN,N-dimethyl-3-diphenylphosphinopropionamide under identical conditionsproduced a liquid phase containing 164 mmole of formaldehyde remaining(42% conversion) with 30.9 mmole glycol aldehyde (26% selectivity) and11.2 mmole methanol (9.2% selectivity).

EXAMPLE 9

The 125 cc stainless steel Parr bomb used in Example 2 was charged with25.0 g sulfolane, 0.75 g paraformaldehyde (23.8 mmole), 0.082 gchlorocarbonylbis (triphenylphosphine)rhodium(I) (0.118 mmole) and 0.061g N,N-dimethyl-3-diphenylphosphinopropionamide (0.213 mmole) which hadbeen sparged with nitrogen. The bomb was then charged with 1600 psi of a1:1 carbon monoxide:hydrogen gas mixture and subsequently heated to 130°C. for 3.0 hours. The bomb was then cooled to room temperature, thegases vented, and the liquid contents analyzed as 10.8 mmoleformaldehyde remaining (55% conv.), 9.1 mmole glycol aldehyde (70%selectivity) and 5.4 mmole methanol (42% selectivity).

COMPARATIVE EXAMPLE 9

A comparative example run under identical conditions as those of example9 except no N,N-dimethyl-3-diphenylphosphinopropionamide was used. Theanalysis of the liquid phase gave 3.8 mmole formaldehyde remaining (84%conversion), 1.75 mmole glycol aldehyde (8.8% selectivity) and 1.63mmole methanol (8.2% selectivity).

EXAMPLE 10

The 300 cc stainless steel autoclave used in Example 1 was charged with100 g acetonitrile, 3.0 g paraformaldehyde (95 mmole), 0.121 gdicarbonylacetylacetonato rhodium (I) (0.469 mmole), 0.054 gtrifluoracetic acid (0.473 mmole), and 0.362 gN,N-dimethyl-3-diphenylphosphinopropionamide (1.27 mmole). The autoclavewas then charged with 1750 psi carbon monoxide and 450 psi hydrogen atroom temperature and heated to 110° C. for 2 hours, whereupon thereactor was cooled and vented. The liquid contents were analyzed for13.3 mmole formaldehyde remaining (86% conversion), 74 mmole glycolaldehyde and 1.2 mmole ethylene glycol (92% selectivity) and 3.4 mmolemethanol (4.2% selectivity).

COMPARATIVE EXAMPLE 10

A comparative example under identical conditions using an equimolarconcentration of triphenylphosphine rather thanN,N-dimethyl-3-diphenylphosphinopropionamide resulted in a liquid phasecontaining 49.3 mmole glycol aldehyde (72% selectivity), 3.9 mmolemethanol (5.6% selectivity) and 25.4 mmole formaldehyde remaining (73%conversion).

EXAMPLE 11

The 300 cc stainless steel autoclave equipped as in Example 1 wascharged with 100 g tetraglyme, 3.0 g of 95% paraformaldehyde (95 mmole),0.121 g dicarbonylacetoacetonato rhodium (I) (0.469 mmole), 0.054 gtrifluoracetic acid (0.470 mmole) and 0.362 gN,N-dimethyl-3-diphenylphosphinopropionamide (1.27 mmole) after anitrogen sparge of the solution. The autoclave was sealed and flushedseveral times with 100 psi carbon monoxide. The autoclave was thencharged with 1750 psi of carbon monoxide and 450 psi hydrogen at roomtemperature. The autoclave and its contents were heated to 110° C. andan initial pressure of 3600 psi. A heated gas reservoir containing thesame carbon monoxide:hydrogen ratio as the autoclave was used to chargethe reaction autoclave when gas absorption lowered the autoclavepressure below 3200 psi. After three hours of reaction, the autoclavewas cooled and vented. Analysis indicated 24.4 mmole formaldehyderemaining (74% conversion), 38.5 mmoles glycol aldehyde and 1.7 mmoleethylene glycol (57% selectivity) and 20.9 mmoles methanol (30%selectivity).

COMPARATIVE EXAMPLE 11

A comparative example under identical conditions with an equimolarconcentration of triphenylphosphone instead ofN,N-dimethyl-3-diphenylphosphinopropionamide resulted in a liquid phasehaving 24.4 mmole formaldehyde remaining (74% conversion), 22.0 mmoleglycol aldehyde and 1.5 mmole ethylene glycol (33% selectivity), and24.1 mmole methanol (34% selectivity).

EXAMPLE 12

The stainless steel autoclave equipped as in Example 1 was charged with100 g acetonitrile, 3.0 g paraformaldehyde (95 mmole), 0.090 gchlorodicarbonyl rhodium (I) dimer (0.232 mmole), 0.057 g4-dimethylaminopyridine (0.464 mmole), and 0.397 gN,N-dimethyl-3-diphenylphosphinopropionamide (1.39 mmole) which had beensparged with nitrogen. The autoclave was charged with 1750 psi carbonmonoxide and 450 psi hydrogen at room temperature and the autoclave andits contents were then heated to 110° C. for three hours. A gasreservoir was used to keep the pressure above 3200 psi, as in Example10. Analysis indicated 5.5 mmole formaldehyde remaining (94%conversion), 64.5 mmole glycol aldehyde and 1.8 mmole ethylene glycol(74% selectivity), and 7.1 mmole methanol (7.9% selectivity).

EXAMPLE 13

The 300 cc stainless steel autoclave equipped as in Example 1 wascharged with 100 g acetonitrile, 9.0 g paraformaldehyde (285 mmole),0.090 g chlorodicarbonylrhodium (I) dimer (0.232 mmole), 0.114 g4-dimethylaminopyridine (0.930 mmole), and 0.397 gN,N-dimethyl-3-diphenylphosphinopropionamide. The autoclave was chargedwith 1500 psi carbon monoxide and 450 psi hydrogen at room temperatureand then heated to 100° C. for one hour. A gas reservoir having the samecarbon monoxide to hydrogen ratio as the autoclave was used to keep thegas pressure above 3200 psi. Upon completion, the autoclave was cooledand the gas vented. Analysis of the liquid solution indicated 89 mmoleof formaldehyde remaining (69% conversion), 155 mmole glycol aldehydeand 1.6 mmole ethylene glycol (80% selectivity) and 21.5 mmole methanol(11% selectivity).

Cobalt and ruthenium were also active for formaldehyde hydroformylation,although less active than rhodium, as is shown in the followingexamples.

EXAMPLE 14

The 300 cc stainless steel autoclave used in Example 1 was charged with6.0 g paraformaldehyde (190 mmole), 100 g acetonitrile, 0.314 gruthenium carbonyl (0.49 mmole), and 0.855 gN,N-dimethyl-3-diphenylphosphinopropionamide (3.00 mmole). The autoclavewas sealed and charged with 1400 psi carbon monoxide and 1350 psihydrogen at room temperature and then heated to 130° C. for 2.0 hours.After cooling and venting, the analysis indicated 57.6 mmoleformaldehyde remaining (70% conversion), 6.2 mmole glycol aldehyde and4.1 mmole ethylene glycol (7.8% selectivity), and 5.3 mmole methanol(4.0% selectivity).

EXAMPLE 15

The 100 cc Parr bomb equipped as in Example 2 was charged with 25 gacetonitrile, 0.75 g paraformaldehyde (23.8 mmole), 0.240 g dicobaltoctacarbonyl (0.696 mmole), and 0.401 gN,N-dimethyl-3-diphenylphosphinopropionamide (1.39 mmole). The bomb wassealed and flushed twice with a 1:1 carbon monoxide:hydrogen mixture.The bomb was then charged with 1500 psi of the gas mixture, whereuponthe autoclave and its contents were heated to 130° C. for 3.0 hours,cooled to room temperature and vented. The liquid contents were analyzedas 7.21 mmoles formaldehyde remaining (69% conversion), 2.92 mmolesglycol aldehyde (18% selectivity) and 0.08 moles methanol (0.5%selectivity).

Preparation of N-methyl-N-octadecyl-3-diphenylphosphinopropionamide[PPh₂ CH₂ CH₂ C(O)N(CH₃)(C₁₈ H₃₇)]

A mixture of 5.7 g ethyl-3-diphenylphosphinopropionate (9.9 mmoles), 5.1g N-methyl-n-octadecylamine (18.0 mmoles), and 0.3 g sodium methoxide(5.6 mmoles) were first deoxygenated and then heated to 100° C. under anitrogen atmosphere for 24 hours. The mixture was then cooled andextracted with pentane. The pentane soluble was rotovapped to an oil.

Infrared analysis displayed a strong, broad γ (CO) band at 1650 cm⁻¹.The elemental analysis was the following: calculated (found); C, 77.94(76.98); H, 10.42 (9.83); P, 5.92 (6.00); N, 2.67 (2.66). The ¹ H NMRshowed a multiplet at 2.3-2.5δ with a relative area of 4 assigned to theCH₂ CH₂ C(O) group, a multiplet at 2.9-3.4δ with a relative area of 5assigned to the N(CH₃)(CH₂)- group, a multiplet at 0.8-1.8δ of relativearea 35 assigned to the C₁₇ H₃₅ alkyl chain, and a multiplet at 7.1-7.8δof relative area of 10 assigned to the P(C₆ H₅)₂ group.

EXAMPLE 16

A 300 cc stainless steel autoclave equipped with a stirrer,thermocouple, and cooling coil was charged with 65 g acetonitrile, 30 gm-xylene, 5 g diethyl ether, 9.0 g of 95% paraformaldehyde (285 mmole ofequivalent formaldehyde), 0.121 dicarbonylacetylacetonato rhodium (I)(0.469 mmole), 0.055 g trifluoroacetic acid (0.482 mmole), and 0.782 gN-methyl-N-octadecyl-3-diphenylphosphinopropionamide (1.39 mmole) whichhad been sparged with dry nitrogen. The autoclave was sealed and the airwas further removed by flushing the autoclave three times with carbonmonoxide at 100 psi. The autoclave was then charged with 1750 psi carbonmonoxide and 450 psi hydrogen at room temperature. A 2-liter autoclavereservoir was also charged with these same gas pressures and heated to270° C. to a total pressure of 3900 psi. The reactor autoclave washeated to 110° C. for 3.0 hours to a total pressure of 3800 psi. Whengas uptake lowered the pressure to 3600 psi, gas was transferred fromthe reservoir autoclave to the reactor autoclave during the run.Analysis of the liquid products by gas chromotography and high pressureliquid chromotography revealed 104 mmole formaldehyde remaining (64%conversion), 165 mmole glycol aldehyde and 4 mmole ethylene glycol (93%selectivity), 6 mmole glyceraldehyde (3% selectivity), and 6 mmolemethanol (3% selectivity).

The glycol products and remaining formaldehyde were separated from therhodium catalyst by first distilling the volatiles (acetonitrile,diethyl ether, trifluoroacetic acid) with a 5 plate 3/8" diameterOldershaw column at a 1:1 reflux ratio with 180 mm Hg pressure under acarbon monoxide sparge at 45°-60° C. The glycol aldehyde and remainingformaldehyde precipitated into a separate oily layer when the volatileswere removed. The orange rhodium catalyst remained in the m-xylene layerwhich was decanted. The last traces of m-xylene in the glycol aldehydewere washed with 5 g of diethyl ether which was separated from the othervolatiles in a subsequent step. The similar densities of m-xylene andglycol aldehyde makes this necessary. Rhodium analysis of the glycolaldehyde layer showed 86 ppm Rh. The excess formaldehyde was distilledto give pure glycol aldehyde.

FIRST RECYCLE

The combined m-xylene and diethyl ether with the soluble rhodiumcatalyst from the first cycle were again combined with 9.0 g 95%paraformaldehyde, 0.055 g (0.482 mmole) trifluoroacetic acid, 65 gacetonitrile, charged into the autoclave, and reacted at 110° C. for 3.0hours as before. Analysis of the liquid products revealed 140 mmole offormaldehyde remaining (51% conversion) with 142 mmole of glycolaldehyde and 2 mmole of ethylene glycol (99% selectivity), and 1 mmoleof methanol (1% selectivity). The volatile acetonitrile and diethylether were distilled off as before to precipitate the glycol aldehydeand remaining formaldehyde. The rhodium catalyst remained in them-xylene layer. The glycol aldehyde layer was washed with diethyl etheras before and finally it was combined with the m-xylene. Atomicabsorption indicated 95 ppm rhodium in the glycol aldehyde layer.

SECOND CYCLE

The recycled m-xylene and diethyl ether with the soluble rhodiumcatalyst were again combined with 9.0 g 95% paraformaldehyde (285mmole), 0.055 g trifluoroacetic acid (0.482 mmole), 65 g acetonitrileand reacted in the same way as before. Analysis of a liquid sampleindicated 131 mmole of formaldehyde remaining (54% conversion) with 145mmole of glycol aldehyde and 2.8 mmole of ethylene glycol (96%selectivity), and 3.1 mmole of methanol (20% selectivity). The volatileswere distilled in the same way precipitating glycol aldehyde which waswashed with purified diethyl ether as before to wash out the lastremaining rhodium entrained in the glycol aldehyde. Analysis of theglycol aldehyde layer by atomic absorption indicated 34 ppm rhodium.

THIRD CYCLE

The m-xylene-diethyl ether solvent mixture with the rhodium catalyst wasagain combined with 0.054 g trifluoroacetic acid (0.474 mmoles), 9.0 g95% paraformaldehyde (285 mmole equivalent formaldehyde), 65 gacetonitrile and charged into the autoclave at the above conditions.Analysis of the liquid products revealed 154 mmole of formaldehyderemaining (46% conversion), 127 mmole of glycol aldehyde and 2.3 mmoleof ethylene glycol (99% selectivity) and no detectable methanol.Analysis of the glycol aldehyde layer by atomic absorption aftercatalyst separation as above indicated 64 ppm rhodium.

FOURTH RECYCLE

The recovered rhodium catalyst in the m-xylenediethyl ether solventmixture was again combined with 0.055 trifluoroacetic acid (0.482mmole), 9.0 g 95% paraformaldehyde, (285 mmole), 65 g acetonitrile andcharged into the autoclave under the above conditions. Analysis of theliquid products after reaction revealed 170 mmole of formaldehyderemaining (40% conversion), 101 mmole of glycol aldehyde (88%selectivity) and no detectable methanol. The glycol aldehyde wasseparated from the rhodium catalyst as before and 96 ppm rhodium wasmeasured in the glycol aldehyde by atomic absorption. In principle thecatalyst could be recycled many more times in the same manner.

COMPARATIVE EXAMPLE 16

The 300 cc stainless steel autoclave was charged with 65 g acetonitrile,30 g m-xylene, 5 g diethyl ether, 9.0 g 95% paraformaldehyde (285 mmoleof equivalent formaldehyde), 0.121 g dicarbonylacetylacetonato rhodium(I) (0.469 mmole), 0.054 g trifluoroacetic acid (0.474 mmole), and 0.397g N,N-dimethyl-3-diphenylphosphinopropionamide (1.39 mmole) which hadbeen sparged with dry nitrogen. The autoclave was sealed and thereaction was carried out under identical conditions to Example 1.Analysis of the liquid products by gas chromatography and high pressureliquid chromatography revealed 59 mmole of formaldehyde (79%conversion), 185 mmole of glycol aldehyde and 2 mmole of ethylene glycol(83% selectivity), 8 mmole of glyceraldehyde (4% selectivity), and 8mmole of methanol (4% selectivity).

The glycol products and formaldehyde were separated from the rhodiumcatalyst by first distilling the volatiles with a 5 plate 3/8" diameterOldershaw column at a 1:1 reflux ratio with 180 mm Hg pressure under acarbon monoxide sparge at 45°-60° C. The glycol aldehyde and remainingformaldehyde precipitated when the volatiles were removed. Both them-xylene and the oily layer of glycol aldehyde and unreactedformaldehyde were red in color. Determination of rhodium in the glycolaldehyde layer revealed 2100 ppm rhodium by atomic absorption.

FIRST RECYCLE

The m-xylene solution with rhodium catalyst was combined with 5 gdiethyl ether, 65 g acetonitrile, and 9.0 g 95% paraformaldehyde (285mmole equivalent formaldehyde) and charged into the 300 cc autoclave asbefore. It was reacted under identical conditions to the first cycle.After cooling, the analysis of the liquid products revealed 182 mmoleformaldehyde left (36% conversion) with 70 mmole of glycol aldehyde (68%selectivity) and 20 mmole methanol (19% selectivity). Only 180 psi Rh(measured by atomic absorption) was still in the liquid solution.

Other rhodium catalyst precursors could be recycled in a similar mannerwith the lipophilic phosphine co-catalyst.

EXAMPLE 17

The 300 cc stainless steel autoclave in Example 1 was charged with 65 gacetonitrile, 30 g m-xylene, 5 g diethyl ether, 9.0 g 95%paraformaldehyde (285 mmole of equivalent formaldehyde), 0.092 gchlorodicarbonylrhodium (I) dimer (0.24 mmole) and 0.737 gN-methyl-N-octadecyl-3-diphenyl phosphinopropionamide (1.41 mmole) whichhad been sparged with dry nitrogen. The autoclave was sealed and flushedthree times with carbon monoxide at 100 psi. The autoclave was thencharged with 1750 psi carbon monoxide and 450 psi hydrogen at roomtemperature. The reactor autoclave was heated to 120° C. for 3.0 hoursto a total pressure of 3600 psi. When gas uptake lowered the pressure to3300 psi, gas was transferred from a reservoir autoclave to the reactorautoclave. After the reactor was cooled and vented, analyses of theliquid products by gas and high pressure liquid chromotography revealed58 mmole of formaldehyde (80% conversion), 152 mmole of glycol aldehydeand 4 mmole of ethylene glycol (69% selectivity), 18 mmole ofglyceraldehyde (8% selectivity), and 31 mmole of methanol (14%selectivity).

The glycol products and remaining formaldehyde were separated from therhodium catalyst by first distilling the volatiles (acetonitrile,diethyl ether, trifluoroacetic acid, methanol) as in Example 1. Theglyceraldehyde, glycol aldehyde and remaining formaldehyde separatedinto a separate oily phase when the volatiles had been removed. Them-xylene solution in which the rhodium catalyst was dissolved wasdecanted. Atomic absorption of the glycol aldehyde mixture revealed 24ppm rhodium.

FIRST RECYCLE

The m-xylene solvent mixture with the rhodium catalyst from the firstcycle was combined with 9.0 g 95% paraformaldehyde (285 mmoles), 5 gdiethyl ether, 65 g acetonitrile, and reacted at 120° C. for 3.0 hoursas before.

After cooling and venting, analysis of the liquid products revealed 116mmole formaldehyde remaining (59% conversion), 122 mmole glycol aldehydeand 2 mmole ethylene glycol (73% selectivity), 10 mmole glyceraldehyde(6% selectivity), and 15 mmole methanol (9% selectivity). The volatileswere removed to separate the m-xylene layer containing the solublerhodium catalyst from the organic reactants and products. Atomicabsorption of the glycol aldehyde layer revealed 12 ppm rhodium.

SECOND RECYCLE

The m-xylene with the rhodium catalyst was combined with 5 g diethylether, 65 g acetonitrile, and 9.0 g paraformaldehyde (285 mmoleformaldehyde). The mixture was purged with nitrogen, charged into theautoclave in Example 1, and reacted at 120° C. for 3.0 hours under thesame carbon monoxide-hydrogen pressures as before. The vessel wascooled, vented, and the volatiles removed as before. Analysis of theliquid phase revealed 122 mmole of formaldehyde remaining (57%conversion) with 107 mmole glycol aldehyde and 1 mmole ethylene glycol(66% selectivity), 5 mmole glyceraldehyde (3% selectivity), and 4 mmolemethanol (2% selectivity). Atomic absorption of the glycol aldehydelayer revealed 66 ppm rhodium. The remainer was in the m-xylene phase asbefore.

THIRD RECYCLE

The m-xylene with the rhodium catalyst was combined with 5 g diethylether, 65 g acetonitrile, and 9.0 g paraformaldehyde (285 mmole). It wasagain charged into the autoclave in Example 1 and reacted at 120° C.under the same pressure of carbon monoxide-hydrogen for 3.0 hours.Analysis of the liquid products revealed 140 mmole for formaldehyderemaining (51% conversion), 84 mmole of glycol aldehyde (58%selectivity), 1 mmole of glyceraldehyde (1% selectivity), and 1 mmole ofmethanol (1% selectivity).

In principle, the same technique could be used to recycle the rhodiumcatalyst many times.

The following comparative examples are comparisons with certain examplesof U.S. Pat. No. 4,405,814 which incorporate an amine and a tertiaryorganophosphorous moiety in its reaction system.

EXAMPLE 18

A 300 cc stainless steel autoclave equipped with a mechanical stirrerthermocouple, and cooling coil was charged with 0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.35 g (N,N-dimethylaminopropyl)diphenylphosphine (1.28 mmole), 9.0 g of 95% paraformaldehyde (285mmoles of equivalent formaldehyde), and 100 g acetone, which weresparged with dry nitrogen. The autoclave was sealed and the air wasfurther removed by flushing the autoclave three times with carbonmonoxide at 100 psi. It was then charged with 2200 psi of a 1:1 mixtureof carbon monoxide and hydrogen. The reactor autoclave was heated to110° C. for 1.4 hours at a total pressure of 2500 psi. When the gasuptake lowered the gas pressure to 2350 psi, the 1 to 1 gas mixture wastransferred from a reservoir autoclave to the reactor autoclave duringthe run. Upon completion, the autoclave was cooled to room temperatureand slowly vented at 0° C. Gas and liquid chromatographic analyses ofthe liquid products revealed 40 mmoles formaldehyde remaining (86%conv), 128 mmoles glycol aldehyde and 6 mmoles ethylene glycol (55%select.), 88 mmoles methanol (36% selectivity) and 9% selectivity tohigh boiling products.

EXAMPLE 19 Presence of a Triphenylphosphine

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.34 g(N,N-dimethylaminopropyl)diphenylphosphine (1.28 mmole) 1.33 gtris(p-fluorophenylphosphine) (4.2 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), and 100 gacetone. Products identified after 1.2 hours were 55 mmoles formaldehyderemaining (81% conversion), 123 mmoles glycol aldehyde and 4 mmolesethylene glycol (55% selectivity), 69 mmoles methanol (30% selectivity)and 15% selectivity to high boiling products.

EXAMPLE 20 Presence of a Different Phosphine-amine

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.36 g(N-pyrrolidine-N-ethyl) diphenylphosphine (1.28 mmoles), 1.33 gtris(p-fluorophenylphosphine) (4.20 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), and 100 gacetone. Products identified after 1.4 hours were 87 mmoles formaldehyderemaining (69% conversion), 140 mmoles glycol aldehyde and 7 mmolesethylene glycol (74% selectivity), 44 mmoles methanol (22% selectivity),and 4% selectivity to high boiling products.

EXAMPLE 21 Presence of Another Phosphine-amine

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.37 g(N,N-dimethylaminobutyl) diphenylphosphine (1.28 moles), 1.33 gtris(p-fluorophenylphosphine) (4.2 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), and 100 gacetone. Products identified after 1.2 hours were 11 mmoles formaldehyde(96% conversion), 122 mmoles glycol aldehyde and 8 mmoles ethyleneglycol (47% selectivity), 81 mmoles methanol (29% selectivity), and 22%selectivity to high boiling products.

COMPARATIVE EXAMPLE 22

Similar to the preceding four examples with the materials charged to theautoclave being 0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole),0.13 g triethylamine (1.28 mmole), 1.33 g tris (p-fluorophenylphosphine)(4.20 mmoles), 9.0 g, of 95% paraformaldehyde (285 mmoles of equivalentformaldehyde), and 100 g acetone. Products identified after 1.2 hourswere 11 mmoles formaldehyde remaining (96% conversion), 147 mmolesglycol aldehyde and 8 mmoles ethylene glycol (56% selectivity), 17mmoles methanol (6% selectivity) and 38% selectivity to high boilingproducts.

EXAMPLE 23 Addition of Water

Similar to Example 19, except that 5.1 g water (278 mmoles) was alsoadded to the autoclave. Products identified after 1.5 hours were 52mmoles formaldehyde (82% conversion), 88 mmoles glycol aldehyde and 10mmoles ethylene glycol (42% selectivity), 138 mmoles methanol (59%selectivity) and no high boiling products.

EXAMPLE 24 Addition of Water

Similar to example 20, except that 5.1 g water (278 mmoles) was againadded. The products identified after 1.7 hours at 110° C. were 62 mmolesformaldehyde remaining (78% conversion), 102 mmoles glycol aldehyde and12 mmoles ethylene glycol (51% selectivity), 72 mmoles methanol (32%selectivity) and 17% selectivity to high boiling products.

EXAMPLE 25 Addition of Water

Similar to Example 21, except 5.1 g water (278 mmoles) was added. Theproducts identified after 1.7 hours at 110° C. were 4.2 mmolesformaldehyde left (99% conversion), 79 mmoles glycol aldehyde and 14mmoles ethylene glycol (33% selectivity), 119 mmoles methanol (42%selectivity), and 25% selectivity to high boiling products.

COMPARATIVE EXAMPLE 26

Similar to the comparative Example 22, except 5.1 g water (278 mmoles)was added to the reaction system. The products identified after 1.5hours at 110° C. were 5 mmoles formaldehyde remaining (98% conversion),118 mmoles glycol aldehyde and 10 mmoles ethylene glycol (46%selectivity), 24 mmoles methanol (9% selectivity) and 45% selectivity tohigh boiling products.

EXAMPLE 27 Increased Water Addition

Similar to Example 21, except that 8.6 g (475 mmoles) water was added.The products identified after 1.5 hours at 110° C. were 4 mmolesformaldehyde remaining (99% conversion), 74 mmoles glycol aldehyde and13 mmoles ethylene glycol (31% selectivity), 165 mmoles methanol (59%selectivity), and 10% selectivity to high boiling products.

COMPARATIVE EXAMPLE 28

Similar to the comparative Example 22, except that 8.6 g water (475mmoles) was added. The products identified after 1.5 hours at 110° C.were 6 mmoles formaldehyde remaining (98% conversion), 89 mmoles glycolaldehyde and 8 mmoles ethylene glycol (35% selectivity), 29 mmolesmethanol (10% selectivity) and 55% selectivity to high boiling products.

EXAMPLE 29 Polar-Non Polar Solvent Mixture

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.35 g(N,N-dimethylaminopropyl) diphenylphosphine (1.28 mmoles), 1.33 gtris-(p-fluorophenyphosphine (4.2 mmoles), 9.0 g of 95% paraformaldehyde(285 mmoles of equivalent formaldehyde), 80 g acetone and 20 g toluene.Products identified after 1.7 hours at 110 degrees C. were 12 mmolesformaldehyde remaining (95% conversion), 127 mmoles glycol aldehyde and3 mmoles ethylene glycol (49% selectivity), 75 mmoles methanol (27%selectivity), and 24% selectivity to high boiling products.

EXAMPLE 30 Mixture of Phosphine-amine and Phosphine-amide

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmoles), 0.24 g(N-pyrrolidine-N-ethyl) diphenylphosphine (0.85 mmoles), 0.23 gN,N-dimethyl-3-diphenylphosphinopropionamide (0.80 mmole), 1.33 gtris-p-fluorophenylphosphine, (4.20 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde) and 100 gacetone which were sparged with dry nitrogen. The products identifiedafter 1.5 hours at 110° C. were 27 mmoles formaldehyde remaining (91%conversion), 152 mmoles glycol aldehyde and ethylene glycol (61%selectivity), 53 mmoles methanol (20% selectivity), and 19% selectivityto higher boiling products.

EXAMPLE 31 Low Pressure System

Similar to Example 30, except that 750 psi carbon monoxide and 750 psihydrogen pressure were present at 110° C. The products identified after1.5 hours at 110 degrees C. were 40 mmoles formaldehyde remaining (86%conversion), 132 mmoles glycol aldehyde and 5 mmoles ethylene glycol(56% selectivity), 63 mmoles methanol (26% selectivity), and 18%selectivity to higher boiling products.

EXAMPLE 32 Acetonitrile Solvent

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.35 g(N,N-dimethylaminopropyl) diphenylphosphine (1.28 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), and 100 gacetonitrile which had been sparged with dry nitrogen. Productsidentified after 1.0 hours at 110° C. were 55 mmoles formaldehyderemaining (81% conversion), 57 mmoles glycol aldehyde and 7 mmolesethylene glycol (28% selectivity), 140 mmoles methanol (61%selectivity), and 11% selectivity to higher boiling products.

COMPARATIVE EXAMPLE 33

Similar to Example 32, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.33 gtriphenylphosphine (1.28 mmoles), 0.13 g triethylamine (1.28 mmoles),9.0 g of 95% paraformaldehyde (285 mmoles of equivalent formaldehyde),and 100 g acetonitrile. Products identified after 2 hours at 110° C.were 42 mmoles formaldehyde remaining (85% conversion), 15 mmoles glycolaldehyde and 15 mmoles ethylene glycol (12% selectivity), 48 mmolesmethanol (20% selectivity) and 68% selectivity to higher boilingproducts.

EXAMPLE 34 Tetraglyme Solvent

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.35 g(N,N-dimethylaminopropyl) diphenylphosphine (1.28 mmoles), 1.33 gtris(p-fluorophenyl) phosphine (4.20 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles), and 100 g tetraglyme. Products identifiedafter 1.5 hours at 110° C. were moles formaldehyde remaining (83%conversion), 97 mmoles glycol aldehyde and 6 mmoles ethylene glycol (43%selectivity), 19 mmoles of methanol (8% selectivity) and 49% selectivityto higher boiling products.

EXAMPLE 35 Heavy Amide Solvent

Similar to Example 18, with the materials charged to autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.35 g(N,N-dimethylaminopropyl) diphenylphosphine (1.28 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), and 100 gN,N-dibutylformamide sparged with nitrogen at room temperature. Productsidentified after 2.0 hours at 110° C. were 28 moles formaldehyderemaining (90% conversion), 112 moles of glycol aldehyde and 16 mmolesof ethylene glycol (49% selectivity), 41 mmoles of methanol (16%selectivity), and 35% selectivity to higher boiling products.

COMPARATIVE EXAMPLE 36

Similar to Example 35, except that the materials charged to theautoclave were 0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole),0.13 g triethylamine (1.28 mmoles), 0.34 g triphenylphosphine (1.28mmole), 9.0 g of 95% paraformaldehyde (285 mmoles of equivalentformaldehyde), and 100 g N,N-dibutylformamide sparged with nitrogen atroom temperature. Products identified after 2.0 hours at 110° C. were 41mmoles formaldehyde (86% conversion), 35 mmoles glycol aldehyde and 5mmoles of ethylene glycol (17% selectivity), 18 mmoles of methanol (7%selectivity), and 76% selectivity to higher boiling products.

EXAMPLE 37 Addition of Methanol

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.12 gN-pyrrolidine-N-ethyl diphenylphosphine (0.42 mmoles), 1.33 g tris(p-fluorophenylphosphine) (4.20 mmoles), and 0.23 gN,N-dimethyl-3-diphenylphosphinopropionamide (0.80 mmoles), 9.0 g of 95%paraformaldehyde (285 mmoles of equivalent formaldehyde), 4.30 gmethanol (134 mmoles), and 100 g acetone which were sparged with drynitrogen. The products identified after 1.5 hours at 110° C. were 38mmoles formaldehyde remaining (87% conversion), 105 mmoles glycolaldehyde and ethylene glycol (43% selectivity), 66 mmoles methanol (27%selectivity) and 30% selectivity to higher boiling products.

EXAMPLE 38 Addition of Methanol--Water

Similar to Example 18, with the materials charged to the autoclave being0.08 g chlorodicarbonylrhodium (I) dimer (0.21 mmole), 0.36 g(N-pyrrolidine-N-ethyl) diphenylphosphine (1.28 mmoles), 1.33 g tris(p-fluorophenylphosphine) (4.20 mmoles), 9.0 g of 95% paraformaldehyde(285 mmoles of equivalent formladehyde), 80 g acetone, 20 g toluene,5.80 g methanol (181 mmoles), and 1.60 g water (89 mmoles) which weresparged with dry nitrogen. The products identified after 1.0 hour at110° C. were 35 mmoles formaldehyde remaining (88% conversion), 127mmoles glycol aldehyde and ethylene glycol (51% selectivity), 42 mmolesmethanol (17% selectivity) and 32% selectivity to higher boilingproducts.

I claim:
 1. A process for the preparation of glycol aldehyde comprisingcontacting formaldehyde, carbon monoxide and hydrogen in the presence ofan organic solvent selected from the group consisting of effective polarand non-polar solvents and a metal catalyst complex, undersuperatmospheric pressures and elevated temperatures; the metal catalystcomplex having the formula:

    MX.sub.w (CO).sub.x [P(R.sub.1).sub.2 R.sub.2 --NR.sub.3 R.sub.4 ].sub.y [P(R.sub.5).sub.3 ].sub.z

wherein M is a metal selected from the group of rhodium, cobalt,ruthenium and mixtures thereof, x is an anion selected from the groupconsisting of halides, pseudohalides, hydrides and deprotonated strongcarboxylic acids; P is phosphorus; R₁ contains 1-20 carbon atoms and isselected from the group consisting of aromatic, aliphatic and mixedgroups; R₂ contains 1-20 carbon atoms and is selected from the groupconsisting of alkyl, aryl and alkaryl groups, and said groups are eitherunsubstituted, or substituted with oxygen, nitrogen and sulfur atoms; R₃and R₄ contain 1-100 carbon atoms and are selected from the groupconsisting of hydrogen, aliphatic, aromatic and mixed groups; w rangesfrom 0-3, x ranges from 1-5, y ranges from 1-4, z ranges from0-3,separating the glycol aldehyde from the reaction mixture.
 2. Aprocess as claimed in claim 1 wherein carbon monoxide and hydrogen arepresent in mole ratios ranging from 20 to 1 to 1 to 20 CO/H₂.
 3. Aprocess as claimed in claim 1 wherein the superatmospheric pressuresrange from about 1000-3000 psia.
 4. A process as claimed in claim 1wherein the elevated temperatures range from about 50° to 150° C.
 5. Aprocess as claimed in claim 1 wherein M is rhodium.
 6. A process asclaimed in claim 1 wherein X is an anion selected from the group ofchlorides, hydrides, and trifluoroacetates.
 7. A process as claimed inclaim 1 wherein R₁ contains 6-10 carbons of aromatic character.
 8. Aprocess as claimed in claim 1 wherein R₂ is aliphatic and comprised ofonly carbon and hydrogen atoms.
 9. A process as claimed in claim 1wherein R₂ contains from 2 to 4 carbon atoms.
 10. A process as claimedin claim 1 wherein at least one of R₃ and R₄ range from about 1 to about20 carbon atoms.
 11. A process as claimed in claim 1 wherein R₃ and R₄are aliphatic in nature and comprised of only carbon and hydrogen atoms.12. A process as claimed in claim 1 wherein the phosphine-amine to metalratio ranges from about 4 to 1 to 1 to
 1. 13. A process as claimed inclaim 1 wherein R₅ ranges from about 6-50 carbons of aromatic character.14. A process as claimed in claim 1 wherein an additionalorganophosphine group is incorporated into at least one of the R₃ and R₄groups.
 15. A process as claimed in claim 1 wherein the catalyst complexexhibits a substantial solubility in non polar organic solvents, therebysubstantially improving the glycol aldehyde product and catalystseparation and recycling operations.
 16. A process as claimed in claim 1wherein the non polar organic solvent is selected from the group oftoluene, xylene, and mixtures thereof.